CN102190896B - Method for recycling waste electronic circuit board and recycled asphalt by using same - Google Patents
Method for recycling waste electronic circuit board and recycled asphalt by using same Download PDFInfo
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- CN102190896B CN102190896B CN2010101244679A CN201010124467A CN102190896B CN 102190896 B CN102190896 B CN 102190896B CN 2010101244679 A CN2010101244679 A CN 2010101244679A CN 201010124467 A CN201010124467 A CN 201010124467A CN 102190896 B CN102190896 B CN 102190896B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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Abstract
The invention provides a method for recycling a waste electronic circuit board, which comprises the following steps: (a) pulverizing the waste electronic circuit board of which the elements are removed, thereby obtaining a metal part and a powdery resin part, wherein the mass content of metal in the powdery resin part is lower than 5%; (b) mixing the powdery resin and asphalt to obtain a mixture, wherein the powdery resin accounts for 1-20% of the asphalt by mass; and carrying out asphalt modification reaction on the mixture at 140-220 DEG C to obtain the modified asphalt. The invention provides a technology for separating resin from a waste PCB (printed circuit board) and a technology for modifying asphalt by using the resin, and solves the problems of too much resin, difficulty in utilization, low economic benefit, environmental protection, asphalt modification and the like.
Description
Technical field
The industrial solid castoff that the present invention relates to a kind of field of environment protection is processed, particularly the pitch that obtains of the recovery method of a kind of waste electronic wiring board (pcb board) and recovery thereof.
Background technology
In waste electronic wiring board (pcb board), nonmetal up to about 60%, main component is thermosetting epoxy resin, filler and glass fibre.Because in recent years, most researchers pays attention to reclaiming the metal part in the pcb board, and less to the resin recycling that occupies a large amount of compositions, resin is that a kind of superpolymer is difficult to by natural degradation, therefore cause secondary pollution to environment, to develop these resins necessary for this reason.
The road bitumen that the crude oil of present China more than 80% is produced contains colloid, bituminous matter is few, contain saturated minute and divide high with fragrance, penetration of bitumens and softening temperature are low, import high-quality heavy oil asphalt (asphalt content is higher) is very expensive, in order to satisfy Road construction to the high-quality asphalt demand, the admixture polymkeric substance carries out modification to pitch in existing road asphalt, has become the important means of improving bitumen properties.
It is faster asphalt modification technology of current development that the research resin is dosed properties-correcting agent, material by adding other is to increase the character of pitch, in the asphalt adhesive body structure, add superpolymer and play similar bitum effect, in the adsorptive pitch saturated minute, fragrance minute and the wax material that grades, both played bitum effect, can reduce again wax and divide negative impact to asphalt performance, the high temperature performance of pitch is all had greatly improved, and its temperature stability also has good raising and reservation or has increased adhesivity, elasticity and the flowability of pitch.The polymkeric substance that is used for asphalt modification generally is divided into elastomerics and plastomer, and elastomerics mainly comprises styrenic block copolymer.After unloading, can get back to original shape such as elastomericss such as styrene-butadiene-styrene (SBS), styrene-isoprene-phenylethene (SIS), vinylbenzene-polyethylene/butyl-polyethylene (SE/Bs) and styrene-butadiene rubber(SBR) (SBR) and can resist tension set; Plastomer mainly comprises ethane-acetic acid ethyenyl fine wine multipolymer (EVA), polyethylene (PE), Atactic Polypropelene (APP) and ethylene-propylene rubber(EPR) (EPDM) etc.Plastomer shows early stage intensity under load, but permanent deformation resistance is good not as elastomerics.The natural rubber modifying asphalt can obtain the ductility of better anti-rut and Geng Gao, but properties-correcting agent is easy to decomposition and oxidized, and the compatibility problem of existence and pitch.SBR is the product of divinyl and styrene monomer random copolymerization, and China has obtained very large progress from the 20 century 70 later stages polymer modified asphalt that begins one's study, but still exists some problems such as anti-rut, water-resistant capacity relatively poor etc.The SBS segmented copolymer is the most a kind of properties-correcting agent SBS of foreign applications.Because the consistency of SBS and pitch is better, and stronger tensile strength is arranged under tension force, SBS has replaced SBR gradually, and SBS is the most frequently used polymer modified asphalt now.SBS has increased the elasticity of pitch, and the SBS modifying asphalt can reclaim, but this properties-correcting agent price is also relatively high.
For this reason, this area in the urgent need to a kind of from discarded pcb board separation resin and resin modified asphalt technology, its objective is solve resin many, utilize that difficulty, economic benefit are low, the problems such as environment protection and asphalt modification.
Summary of the invention
The first purpose of the present invention be to obtain a kind of from discarded pcb board separation resin and resin modified asphalt technology, its objective is solve resin many, utilize that difficulty, economic benefit are low, the problems such as environment protection and asphalt modification.
The second purpose of the present invention is to obtain a kind of pitch that separation resin and resin modified obtain from discarded pcb board.
In a first aspect of the present invention, the recovery method of a kind of waste electronic wiring board (pcb board) is provided, it comprises the steps:
(a) the waste electronic wiring board that will remove components and parts is pulverized separation, obtains metal part and powdery resin part, and metal quality content is lower than 5% in the described powdery resin;
(b) powdery resin is mixed with pitch, described powdery resin accounts for 1～20% of asphalt quality, obtains mixture; Described mixture carries out the asphalt modification reaction under 140～220 ℃, obtain modifying asphalt.
In a specific embodiment of the present invention, adopt the two grade pulverization method to pulverize separation in the described step (a), comprise the steps:
(i) the waste electronic wiring board that will remove components and parts is pulverized in the one-level crusher, until obtain the one-level powder of particle diameter between 10mm～20mm;
(ii) the one-level powder that described step (i) is obtained is pulverized at secondary breaker, until obtain the secondary powder that particle diameter is not more than 0.8mm.
In a specific embodiment of the present invention, comprise that also the secondary powder that described step (ii) is obtained carries out gravity, magnetic separation, electric separation separating metal and nonmetal.
In a preference, will remove the discarded pcb board of components and parts, the application machine physical method pulverizes to realize metal and nonmetal separating with pcb board, wherein the nonmetal overwhelming majority is resin.Pulverize in two steps, the first step is sent into the one-level crusher in crushing to 10mm～20mm with it, again pulverized particles is delivered to secondary breaker and be crushed to 0.8mm, again according to certain physical properties, comprise that gravity, magnetic separation and electric separation separate with resin metal, gold in resin belongs to containing and is lower than 5%, carries out Screening Treatment to nonmetal, chooses 20 order toners with for subsequent use.
In a specific embodiment of the present invention, in the described step (b), choose particle diameter and be not less than 20 purpose powdery resins parts and mix with pitch.
In a specific embodiment of the present invention, the reaction of the asphalt modification of described step (b) comprises the steps:
Described mixture carried out swollen-state polymerization 1 ± 0.5 hour under 140～220 ℃ temperature and mechanical stirring;
Reactant behind the swollen-state polymerization carries out optional shear-mixed emulsification 0～90min, obtains modifying asphalt.
More preferably, carried out swollen-state polymerization 1 ± 0.2 hour.
In a preference, with the powdery resin part, choose as requested the toner of 20 order particle diameters as properties-correcting agent, join and be heated to 120 ℃, and in the pitch of constant temperature 30min, then be heated to 140～220 ℃, and mechanical stirring, beginning swollen-state polymerization 1 hour fully mixes with pitch to toner, then starts high shearing mixing emulsor, time 0～90min, phase time, resin modified end of processing, the amount that wherein adds resin no longer occurring obviously dividing on the top layer to pitch and toner is 1%～20% of asphalt quality.
In a specific embodiment of the present invention, temperature is controlled at 160～200 ℃.
In a specific embodiment of the present invention, temperature is controlled at 180 ± 5 ℃.
In a specific embodiment of the present invention, shear-mixed emulsification 30～60min.
In a specific embodiment of the present invention, shear-mixed emulsification 55～60min.
The modifying asphalt that another aspect of the present invention provides method of the present invention to obtain.
Description of drawings
Fig. 1 is process flow sheet of the present invention.
Embodiment
The inventor is through extensive and deep research; by improving preparation technology; obtained a kind of from discarded pcb board separation resin and resin modified asphalt technology, its objective is solve resin many, utilize that difficulty, economic benefit are low, the problems such as environment protection and asphalt modification.Finished on this basis the present invention.
Design of the present invention is:
The present invention relates to reclaim resin and modifying asphalt method from the waste electronic wiring board, is that discarded pcb board resin is utilized and resource utilization, and a kind of method of performance of modified bitumen.Belong to industrial solid castoff processing, resource utilization field and building materials modification field in the environmental protection technical field.
Below describe in detail to various aspects of the present invention; Specify such as nothing, various raw materials of the present invention all can obtain by commercially available; Or prepare according to the ordinary method of this area.Unless otherwise defined or explanation, same meanings of being familiar with of all specialties used herein and scientific words and those skilled in the art.Any method similar or impartial to described content and material all can be applicable in the inventive method in addition.
The invention provides the recovery method of a kind of waste electronic wiring board (pcb board), it comprises the steps:
(a) the waste electronic wiring board that will remove components and parts is pulverized separation, obtains metal part and powdery resin part, and metal quality content is lower than 5% in the described powdery resin;
(b) powdery resin is mixed with pitch, described powdery resin accounts for 1～20% of asphalt quality, obtains mixture; Described mixture carries out the asphalt modification reaction under 140～220 ℃, obtain modifying asphalt.
Step (a) separating step
In a specific embodiment of the present invention, adopt the two grade pulverization method to pulverize separation in the described step (a), comprise the steps:
(i) the waste electronic wiring board that will remove components and parts is pulverized in the one-level crusher, until obtain the one-level powder of particle diameter between 10mm～20mm;
(ii) the one-level powder that described step (i) is obtained is pulverized at secondary breaker, until obtain the secondary powder that particle diameter is not more than 0.8mm.
In a specific embodiment of the present invention, comprise that also the secondary powder that described step (ii) is obtained carries out gravity, magnetic separation, electric separation separating metal and nonmetal.
In a preference, will remove the discarded pcb board of components and parts, the application machine physical method pulverizes to realize metal and nonmetal separating with pcb board, wherein the nonmetal overwhelming majority is resin.Pulverize in two steps, the first step is sent into the one-level crusher in crushing to 10mm～20mm with it, again pulverized particles is delivered to secondary breaker and be crushed to 0.8mm, again according to certain physical properties, comprise that gravity, magnetic separation and electric separation separate with resin metal, gold in resin belongs to containing and is lower than 5%, carries out Screening Treatment to nonmetal, chooses 20 order toners with for subsequent use.
In such scheme, when separation resin from pcb board, when PCB pulverizes in one-level, pulverizing to 10mm the time, easier being crushed to about 0.8mm during two-stage crushing;
When separation resin from pcb board, when PCB was crushed to 0.8mm, it was 5% that gold in resin belongs to content, because pulverized particles is when very thin, easier tolerant reason is separated;
When separation resin from pcb board, when granular powder is broken to the 0.8mm left and right sides, is conducive to reduce the content that gold in resin belongs to and is lower than below 5%;
Step (b) modification procedure
In a specific embodiment of the present invention, in the described step (b), choose particle diameter and be not less than 20 purpose powdery resins parts and mix with pitch.
In a specific embodiment of the present invention, the reaction of the asphalt modification of described step (b) comprises the steps:
Described mixture carried out swollen-state polymerization 1 ± 0.5 hour under 140～220 ℃ temperature and mechanical stirring;
Reactant behind the swollen-state polymerization carries out optional shear-mixed emulsification 0～90min, obtains modifying asphalt.
More preferably, carried out swollen-state polymerization 1 ± 0.2 hour.
Preferably, the amount of adding resin is 1%～20% of asphalt quality, most preferably 5-15%.
In a preference, with the powdery resin part, choose as requested the toner of 20 order particle diameters as properties-correcting agent, join and be heated to 120 ℃, and in the pitch of constant temperature 30min, then be heated to 140～220 ℃, and mechanical stirring, beginning swollen-state polymerization 1 hour fully mixes with pitch to toner, then starts high shearing mixing emulsor, time 0～90min, phase time, resin modified end of processing, the amount that wherein adds resin no longer occurring obviously dividing on the top layer to pitch and toner is 1%～20% of asphalt quality.
In a specific embodiment of the present invention, temperature is controlled at 160～200 ℃.
In a specific embodiment of the present invention, temperature is controlled at 180 ± 5 ℃.
In a specific embodiment of the present invention, shear-mixed emulsification 30～60min.
In a specific embodiment of the present invention, shear-mixed emulsification 55～60min.
The inventor finds, when the resin modified process, when the addition of resin is 2%～15%, and do not have modifying asphalt to compare its penetration degree, softening temperature, ductility better improvement is all arranged; Pitch control is 5% the time, effect is best, owing to work as dose of polymer hour (below 15%), aromatic hydrocarbon in the pitch can be with polymer dissolution, when dose of polymer is higher (more than 15%), properties-correcting agent swelling behavior variation thereby descend with the interface interaction power of pitch, and the interaction force between the high molecular particle increases, increase along with amount of polymers, the properties-correcting agent particle size increases mutually overlap joint fusion and forms a kind of reticulated structure, the volume of polymkeric substance this moment in pitch is exactly the threshold value that polymkeric substance can form a kind of stable and whippy network structure, be add-on when being 15%, modified system undergoes phase transition, and polymkeric substance is converted into external phase by discontinuous phase, pitch is converted into discontinuous by external phase, will be accompanied by a low temperature brittleness this moment to the transformation of elastic behavior; When PCB amount of powder in being dissolved in pitch increased, the colloidal dispersion of modifying asphalt can develop to gel-type, and its ductility can reduce, and fragility rises, and still, it will descend to temperature sensitivity, so softening temperature begins to descend.It is more that the PCB amount of powder adds, and its colloidal dispersion more levels off to thermosetting material.Softening temperature is when conversion critical amount (15%), and softening temperature descends, and during mainly due to external phase and discontinuous phase conversion, the character sudden change occurred, and after postcritical, system has the steady state of transferring to, the softening temperature bottom out.When a large amount of PCB powder enters in the pitch item by shearing, cause the pitch supersaturation, to the gel-type system transition, so that integral body becomes fragile, ductility descends.If visible under different temperature, the addition of powder rises, and whole ductility is on a declining curve.
The inventor also finds, in such scheme, when the resin modified process, shear blend (also namely the shearing blend emulsification) time when 30～90min, penetration degree, softening temperature, ductility all have better improvement, when being controlled at the 60min left and right sides, reach best effect.
Other aspects of the present invention are because the disclosure of this paper is apparent to those skilled in the art.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example usually according to normal condition, or carries out according to the condition that manufacturer advises.Unless otherwise indicated, otherwise all umbers are weight part, and all per-cents are weight percentage, and described polymericular weight is number-average molecular weight.
Unless otherwise defined or explanation, same meanings of being familiar with of all specialties used herein and scientific words and those skilled in the art.Any method similar or impartial to described content and material all can be applicable in the inventive method in addition.
Embodiment 1
To remove the discarded pcb board of components and parts, the application machine physical method pulverizes to realize metal and nonmetal separating with pcb board, and wherein the nonmetal overwhelming majority is resin.Pulverize in two steps, the first step is sent into the one-level crusher in crushing to 10mm～20mm with it, again pulverized particles is delivered to secondary breaker and be crushed to 0.8mm, again according to certain physical properties, comprise that gravity, magnetic separation and electric separation separate with resin metal, gold in resin belongs to containing and is lower than 5%, carries out Screening Treatment to nonmetal, chooses 20 order toners with for subsequent use.
Pre-treatment 95g pitch: be heated to 120 ℃, and maintenance 30min, sieve the resin of 20 order particle diameters, take by weighing the 5g resin and join in the bituminous solution, be heated to simultaneously 180 ℃, mechanical stirring 1 hour, to pitch and toner mixing end, start high shearing mixing emulsor, shear 60min, reaction process finishes; After testing, softening degree is 60.9 ℃, ductility 9.5cm, and penetration degree is 78.2mm.
Embodiment 2
Pre-treatment 90g pitch, be heated to 120 ℃, and keep 30min, and sieve the resin (such as embodiment 1) of 20 order particle diameters, take by weighing the 10g resin and join in the bituminous solution, be heated to simultaneously 160 ℃, mechanical stirring 1 hour to pitch and toner mixing end, is started high shearing mixing emulsor, shear 60min, reaction process finishes; After testing, softening degree is 58.7 ℃, ductility 8.6cm, and penetration degree is 71.3mm.
Embodiment 3
Pre-treatment 95g pitch, be heated to 120 ℃, and keep 30min, and sieve the resin (such as embodiment 1) of 20 order particle diameters, take by weighing the 5g resin and join in the bituminous solution, be heated to simultaneously 200 ℃, mechanical stirring 1 hour to pitch and toner mixing end, is started high shearing mixing emulsor, shear 30min, reaction process finishes; After testing, softening degree is 68.2 ℃, ductility 8.8cm, and penetration degree is 55.1mm
The above only is preferred embodiment of the present invention, be not to limit essence technology contents scope of the present invention, essence technology contents of the present invention is broadly to be defined in the claim scope of application, any technology entity or method that other people finish, if defined identical with the claim scope of application, also or a kind of change of equivalence, all will be regarded as being covered by among this claim scope.
All quote in this application as a reference at all documents that the present invention mentions, just as each piece document is quoted separately as a reference.Should be understood that in addition after having read foregoing of the present invention, those skilled in the art can make various changes or modifications the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (9)
1. the recovery method of a waste electronic wiring board (pcb board) is characterized in that, comprises the steps:
(a) the waste electronic wiring board that will remove components and parts is pulverized separation, obtains metal part and powdery resin part, and metal quality content is lower than 5% in the described powdery resin;
(b) powdery resin is mixed with pitch, described powdery resin accounts for 2～15% of asphalt quality, obtains mixture; Described mixture carries out the asphalt modification reaction under 140～220 ℃, obtain modifying asphalt;
Wherein said asphalt modification reaction comprises the steps:
Described mixture carried out swollen-state polymerization 1 ± 0.5 hour under described 140～220 ℃ temperature and mechanical stirring;
Reactant behind the swollen-state polymerization carries out shear-mixed emulsification 30～90min, obtains modifying asphalt.
2. the method for claim 1 is characterized in that, adopts the two grade pulverization method to pulverize separation in the described step (a), comprises the steps:
(i) the waste electronic wiring board that will remove components and parts is pulverized in the one-level crusher, until obtain the one-level powder of particle diameter between 10mm～20mm;
(ii) the one-level powder that described step (i) is obtained is pulverized at secondary breaker, until obtain the secondary powder that particle diameter is not more than 0.8mm.
3. method as claimed in claim 2 is characterized in that, comprises that also the secondary powder that described step (ii) is obtained carries out gravity, magnetic separation, electric separation separating metal and nonmetal.
4. the method for claim 1 is characterized in that, in the described step (b), chooses particle diameter and is not less than 20 purpose powdery resins parts and mixes with pitch.
5. the method for claim 1 is characterized in that, temperature is controlled at 160～200 ℃.
6. the method for claim 1 is characterized in that, temperature is controlled at 180 ± 5 ℃.
7. the method for claim 1 is characterized in that, shear-mixed emulsification 30～60min.
8. the method for claim 1 is characterized in that, shear-mixed emulsification 55～60min.
9. modifying asphalt that obtains such as the method for claim 1～8.
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| CN2010101244679A CN102190896B (en) | 2010-03-15 | 2010-03-15 | Method for recycling waste electronic circuit board and recycled asphalt by using same |
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| CN2010101244679A CN102190896B (en) | 2010-03-15 | 2010-03-15 | Method for recycling waste electronic circuit board and recycled asphalt by using same |
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| CN102190896B true CN102190896B (en) | 2013-02-20 |
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| CN102311650B (en) * | 2011-09-29 | 2013-04-10 | 广东工业大学 | Method for modifying asphalt by concurrently using waste printed circuit board pyrolytic oil heavy fractions and styrene butadiene rubber |
| CN102391657B (en) * | 2011-09-29 | 2013-06-12 | 广东工业大学 | Method for modifying asphalt by using pyrolytic oil heavy fraction of waste printed circuit board |
| CN103755189B (en) * | 2013-12-09 | 2017-11-21 | 长安大学 | Electronic waste powder, asphalt and preparation method thereof and conductive road surface |
| CN105655003B (en) * | 2015-12-30 | 2018-08-14 | 安徽枫雅轩科技信息服务有限公司 | A kind of modified electrode paste and preparation method thereof |
| CN106046818A (en) * | 2016-07-06 | 2016-10-26 | 广西民族大学 | Method for preparing modified asphalt by using waste circuit board non-metal powder |
| CN108439408A (en) * | 2018-02-12 | 2018-08-24 | 中山大学 | A method of preparing silicon carbide powder material using circuit base plate is discarded |
| CN111978748B (en) * | 2020-08-27 | 2022-03-04 | 广西大学 | Environment-friendly novel compound modified asphalt for waste batteries and preparation method thereof |
| CN115785683B (en) * | 2022-12-08 | 2024-04-16 | 苏州卓宝科技有限公司 | PCB modified asphalt sizing material and preparation method thereof |
| CN116477883A (en) * | 2023-04-27 | 2023-07-25 | 内蒙古农业大学 | Composition for repairing pavement crack grouting, pavement crack grouting repair material and preparation method thereof |
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